Lect 11-12 Biomineralization_print
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Transcript of Lect 11-12 Biomineralization_print
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MSE 598/494 Bio-inspired Materials and BiomaterialsMSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: [email protected]
2014-04-03
Lecture 11 & 12. Biominerilaztion
Proteins and Organisms
Lecture 11 & 12. Biominerilaztion
Proteins and Organisms
material/composition?
shapes?
Biomineralization
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More and more functions for synthetic materials
Tissue engineering: regenerative biomedical, hard tissue (bone, enamel)
Advanced Materials: Light weight tough material for building, aircraft, vehicle
Nanomaterials : precise control of nano-spheres, rods, wires, tubes, etc3
Nature
producing mineralised skeletons
for the 550 million years
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Nature evolved to grow superior biominerals
Optical sensing (predator) Mechanical tough (protection)
Photonic color Self healing
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Diversity
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Biomineralization
Definition: the process that organisms use biomolecules and biological substances to
assemble organized inorganic scaffolds, often to harden or stiffen existing tissues.
Examples: silicates in algae and diatoms, carbonates in invertebrates, and calciumphosphates and carbonates in vertebrates
Structuresconsiderable variety of structures, morphologies, and shapes of materials
Underlying Molecular Mechanism? directed crystal growth occurring at biomolecular interfaces recruitment of various organic and inorganic building blocks the specific conditions of the aqueous solution environments
Functionsmagnetic sensors in magnetotactic bacteria (Fe3O4),
gravity sensing devices (CaCO3, CaSO4, BaSO4),iron storage and mobilization (Fe2O3H2O in the protein ferritin)
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What you will learn in the next 90 minutes?
Lecture 11. Biomineralization - Proteins
Natural biominerals:Nacre, Bone
Protein Template for Artificial Nacre, Synthetic Bone
Cellular membranes template (option for Lit Rev Presentation)
Lecture 12. Biomineralization - Organisms
Virus:M13 phage, T7 phage
Bacterial Cells Larger organisms
Applications (M13 phage for self-assembly, photovoltaics)(option for Lit Rev Presentation)
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Template:
i) proteins
peptide
ii) viruses
bacteria
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MSE 598/494 Bio-inspired Materials and BiomaterialsMSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: [email protected]
2014-04-03
Lecture 11. Biominerilaztion
Protein- and peptide-associated biomineralization
nacreous layer:
iridescent
strong, resilient, tough
A Story of Nacre
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Fun Fact: Usage of Nacre
Architecture - mosaic with durable and glossy surface
Marble or tile base: nacre tesserae is cut into shapes and laminated toa ceramic tile or marble base
Light weight material: interior floors, exterior and interior walls,countertops, doors and ceilings
Fashion:
Decoration:
Watch
musical instruments
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Pearly Kings and Queens(an organisedcharitable tradition
of working class culture in London)
Delicate Beauty?
Unique properties:
Optical: ~80% total transmission of visible light (window panel)
Mechanical: penetration resistance through a variety of energy-dissipating
mechanisms, by increasing energy dissipation density (0.290 nJ m3) by anorder of magnitude relative to single-crystal geological calcite (0.034 nJ m3)
Ortiz, et al. Nature Materials 2014
pervasive nanoscale deformation twinning
(width ~50 nm)
windowpane oyster (~99 wt% calcite)
a layered assembly of elongated
diamond-shaped calcite crystals
Mechanism: catalyses a series of additional inelastic energy dissipating
mechanisms (intracrystalline nanocracking, nanograin formation and reorientation)
Extremely tough and lightweight armour for US soldier!
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Nacre
A remarkable organicinorganic composite biomaterial
Structure & Composition:Ordered inorganic layers of calcium carbonate platelets separated byporous organic polymers such as chitin
Properties: Optical iridescent sheen
Mechanical tough, resilient to damage, due to highly efficient dissipationof cracks and mechanical stress
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brick wall structure comprising
Ca(CO3) crystals and biopolymer mortar
Mimicking the Biomineralization
Organic Template Inorganic Mineral
1. Biomimetic templates Polyaspartic acid adsorbed on a sulfonated PS film as a scaffold for CaCO3 Langmuir manolayers of fatty acids on aqueous subphases
Self-assembly monolayers (SAMs) on solid substrates
Acidic macromolecules:
Polysaccharides
(glyco)proteins
Aspartatic acid
Glutamic acid
Phophate moities
Calcium carbonate
Silica
apatite
2. Directing Effects
How to induce
Oriented Nucleation
with acidic groups on
surfaces
Carboxylic
Phosphate
Sulfate
3. Precise control ofcomposition,
organization,morphology,
other properties
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Artificial Nacre the toughness
The same structure that gives seashells their strengthhas been replicated in glass
Structure: lasers to create an analogue of nacre by engraving networksof wavy 3D "micro-cracks" in glass.
Property:
Treated glass is 200 times tougher than untreated glass.
Mechanism:when the slides were subjected to an impact, the micro-cracks absorbed and dispersed the energy, keeping the glass from
shattering.
15 Franois Barthelat, et al. Nature Communications 2014
Artificial Nacre the structure
Al2O3 and PMMA
Exceptional strength andtoughness, ascribed to
the specific composition,
the microscopic layered structure ofthe particulates
Launey, M.E. et al.,
Designing highly toughened hybrid composites through natureinspired hierarchical complexity,
Acta Materialia 2009 57, 29192932.16
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Artificial Nacre the growth
The first successful attempt to replicate nacre, using CaCO3 Mimicking the growth composite, structure, and property:
Calcium carbonate-based nacre in the laboratory by mimicking its naturalgrowth process with layer-by-layer assembly
17 Ullrich Steiner, Nature Communications 2012
Artificial Nacre the growth
Polymer-mediated Mineral Growth:
early-stage crystallization throughsingle PVP pores in a trilayer of
calorg/organic/calorg
Ullrich Steiner, Nature Communications 2012
(scale bar: 500 nm)
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Protein- and peptide-associated biomineralization
Acidic Proteins-mineralization templatesNegatively charged amino acids: particularly glutamate (Glu)
Mechanism:
To recruit and bind inorganic cations, such as calcium, thereby initiating themineralization process.
Artificial biomineralization:
Their Nature and Organization Mineral Assembly
Utilize surfaces containing acidic amino acids or negatively-charged
moieties as synthetic templates for artificial biomineralization
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peptide-mimics template - Peptoid
Peptoid structures respectivedistinct CaCO3 crystalmorphologies produced uponincubation of the peptoids with
Ca2+ and sequestered CO2.
Biologically-inducedinorganic materials:
20Chen, C.L. et al., J. Am. Chem. Soc. 2011 133, 52145217.
Biological molecule:
recognition units/domains
nucleation sitesmolecular facets activating crystallizationaid overcoming energy barriers
Non-biological substances bind
Mineral assembly
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Repair and Reconstruction of Tooth Enamel
Enamel: the protective layer of the tooth
Challenge: complex needle-like structure comprising tiny crystallites of apatite; limited
supply of natural enamel-template proteins(enamelins/ameliogenins) as seeding agents
Approach: Regenerated layers of crystalline apatite formed through bridging by thenegatively-charged glutamic acid
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Natural:
crystalline apatite
Ca10(PO4)6(OH)2
Artificial:
Li, L. et al.,Adv. Mater. 2011, 23, 46954701
Bone Formation
Bone formation: similar hierarchical mineralization of calcium and phosphateions forming hydroxyapatite crystals via collagen matrix
physical properties of collagen Bone morphology & internal organization
22Zhang, Z. et al., Applications of functional surfactants,
Curr. Opin. Coll. Interface Sci. 2002 7, 267275.
collagen-mimic peptide-amphiphile fibers:
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The natural growth dynamic environmental cues
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Abrupt switches in marine shell pattern
Hierarchical, complex
Continuously changing chemical cues
Significance & Motivation:
Top-down lithography V.S. bottom-up Shed light on biominerilization process in natural evolution, yet unpredictable Rationally design and actively shape self-assembly by manipulating
microenvironment, epitaxy, inorganic-organic additives, etc. to direct write andsculptarbitrary 3D hierarchical structures
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
Rational Design
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Novel strategy: Exploited to program a variety of elementary
growth patterns:
Ba2+ + CO2 + H2OBaCO3 + 2H+
SiO32+2H+SiO2+H2O
By diffusion of CO2 in a solution of BaCl2 and Na2SiO3 Responsive growth of BaCO3-SiO2 structures, toward or away from the bulk solution
Three reaction regimes under two distinct growth modes: continuous anddiscrete modulations, controlled by CO2 concentration, pH, and temperature
Stems SrCO3-SiO2 (pH 11.8)
tulips BaCO3-SiO2 (4oC, pH 11)
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Rational Design
CO2 Flux:
amount direction (orientation of sample)
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
a combinatorial matrix
of morphologies by
changing the orientation
of the substrate in
distinct growth steps to
stack different
morphologies on top of
each other. (Strontium
Carbonate) SrCO3-SiO2Stem, (BariumCarbonate) BaCO3-
SiO2 vases.
Rational Design
SrCO3-SiO2 vases containing SrCO3-SiO2 stems (green)
- subsequently opened with a CO2 pulse (blue)
Rhythmical pulsing of CO2 in the Ba-Si solution
controllably produces ripples in the growing structures
that can be used to write messages in Morse code.
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MSE 598/494 Bio-inspired Materials and BiomaterialsMSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: [email protected]
2014-04-01
Lecture 12. Biominerilaztion
Organism-templated biomineralization
Organism-templated biomineralization
entire organisms serving as templates
algae, virus and cyanobacteria
bacterially-induced calcification has been proposed as a promising biogenicroute for sequestering atmospheric carbon dioxide and for carbon storage
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Brome mosaic virus (BMV) capsids:
Virus-like particles (VLPs) comprising
different sizes of inorganic cores
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Tobacco mosaic virus (TMV) templated Biomineralization
inorganic deposits grown on the surface of TMV. (a)TMV coatedwith iron oxide, initial product; (b)TMV coated with iron oxide, 6months incubation.
TMV coated with silica; the arrows indicate the lengths of individualviral particles, suggesting head-to-tail arrangement of the viral rods.
29 Shenton, W. et al.,Adv. Mater. 1999 11, 253256.
M13 phage
M13 phage: a bacteria-infecting virus, composed of a single-strandedDNA encapsulated by several coat proteins
30Flynn, C.E. et al., Viruses as vehicles for growth, organization
and assembly of materials,Acta Materialia. 2003 51, 58675880.
coat proteins
binding and nucleation of
different inorganic substances
peptides
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Phage-library for biomineralization templates
Phage-library technology for identification of effective biomineralizationtemplates
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1) A library of recombinant phages,
comprising different peptides
displayed at the phage coat proteins
2) reacted with inorganic substances
3) phages interacting with the inorganic materials,
or inducing mineralization, are isolated
4) most effective biomineralization-inducing
phages are selected and sequenced
Flynn, C.E. et al., Viruses as vehicles for growth, organization and assembly of materials,Acta Materialia. 2003
Liquid crystalline quantum dots through M13 library screening
the phage displaying the peptide with the highest affinity wasisolated and amplified
concentrated solution of the phage-QD complexes adopts a
liquid crystalline organization -- optical and spectroscopicapplications
32Flynn, C.E. et al., Viruses as vehicles for growth, organization and assembly of materials,Acta Materialia. 2003
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T7 bacteriophage
Sphericalviruses, icosahedron-shaped bacteriophage Deposition of inorganic substances can be carried out both externally
on the viral coat and inside the particle.
Ghost viruses comprising the T7
capsids without the encapsulated DNA
Metallic cobalt grown inside
the T7 ghost viruses
Liu, et al. J. Magn. And Magnetic Mater. 2006 302, 4751.33
Microorganisms - bacteria
charged amino acids and other functional groups at the cell surface
after the biomineralization process, the bacterial cells are removed
through annealing (high temperature), leaving behind hollow structures invaried configurations, depending upon the bacterial species encapsulated.
highly uniform ZnO hollow spheres
using the spherical bacterium
Streptococcus thermophilus
Zhou. et al. Micro. Meso. Mater. 2007 100, 322327.34
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Microorganisms - diatoms
ZnS:
Diatoms:
Gordon, R. Star Trek replicators and diatom nanotechnology, Trends Biotech. 2003 21, 325328.35
Larger organisms as templates
sea-urchin skeleton - Au replication butterfly-wing microstructures Al2O3using ALD, for photonic applications
Huang, J. et al., Nano Lett. 2006 6, 23252331.Seshadri R. and Meldrum F. C.,Adv. Mater. 2000 12, 11491151.36
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Summary
Biomineralization:
molecular mechanism structure function
Lecture 11. Proteins templating
Natural biominerals:Nacre, Bone
Protein Template for Artificial Nacre, Synthetic Bone
Cellular membranes template (option for Lit Rev Presentation)
Lecture 12. Organisms templating
Virus:M13 phage, T7 phage
Bacterial Cells Larger organisms
Applications (M13 phage for self-assembly, photovoltaics)(option for Lit Rev Presentation)
37
Reading Resources
Prof. Steve Mann
Prof. Joanna Aizenberg
Are glass sponges made of glass?
tricks for turning its brittle, primarilyglass skeleton into strong structures
double-lens design
Brittlestar calcite single crystals -photodetector
genus Euplectella
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Homework of Lecture 11-12
1. Please state the general mechanisms of biomineralization, bydescribing the roles of organic, inorganic elements and theirinteractions.
Due by 04/08/2014
Hand in hard copy of homework at the TA, Xiying Chen, at thebeginning of the 04/08 class
Please contact [email protected] for questions.